Manufacture of sulphuric esters of anthrahydroquinones



Patented Apr. 18, 1933 i .(UN ED' "STA ES mnnrac'ruan or son-Prisms ESTER-S or ancrnarirrirnrioaulnonnsf No Drawing, ,Application filed March 23, ,1931/ElfirialNo. 524,763, are. in GreatBr itai n March 25, 1930.:

This invention relates to the manufacture of sulphuric esters of anthrahyd'roquinones, and it comprises a process wherein ammonia and alkylamines are reacted With disulphuric esters of 1 halogenohydroanthraquinone-Q-carboxylic acid andits esters, the said disulphuric esters being obtained, if desired, by treating the corresponding halo-n genohydroanthraquinone carboxylic acid or its ester With zinc dust, pyridine and pyridine-sulphuric anhydride; and it further comprises the products so produced particularly the. amino and alkylamino derivatives of the sulphuric esters of anthrahydro quinones. i a a y We have found that new and valuable amino and alkylaminoderivatives of disulphuric esters of anthrahydroquinone-Q-carboxylic acid compounds having the probabl formula: A I or.

H 3s o I IR Boas-t wherein It represents a hydrogen or an alkyl group maylbe produced by reacting amino compounds having the following structural formula: I

HN V \R with the disulphuricesters of l-halogenoanthrahydroquinone-2-carboxylic acid and its esters, having the probable formula:

wherein. X represents a halogen, such as chlorine orbromine. V

The disulphuric ester used in the above processimay be prepared from the c'orre- 5mm Mailman vinxzrn r rRwEA'rHEB, wan-K131154111 romvrolvn'rsoo'rnann; assmrrons To IMPERIAL AVCQRPORA'TION OF GREAr B-ITAIN;

crrn-MIcAr. mnnsrmns IMITE spending 1-halogenoanthraquinonecarboxylacid or its ester by treatment with zinc, dust, pyridine and pyridine sulphuric ant V hydride. The disulphuric ester compound so produced may be converted into the. amino i and alkylamino compound of'the type given ante by heating it with ammonia, or primary and secondary alkylamines, For instance tives may be dia'zotized, and coupled with;

v phenols and like. coupling components-to givevaluableazo compounds. They are val;

uable in the preparation: of ,dyestufis or {in-.1

termediates. For instance, theyi ma y be diazotized and coupled b thefimethod i'de-f applications 423,-

scribed in cop'ending U. l 1 79 and 426,417. 1w V The following examples illustrate our-in ventionas applied-to the production vofi amino and methylamino derivatives, but sit Will be understood that theseareby no means limitative. ,In the-examples the parts' lare parts by Weight.

; Eamail I parts I of 1-chloranthraquinone Q-carQa boxylic acid are mixed With 6O .partsrsof. pyridine sulphur trioxide andIOQ parts of,

pyridine. The mixture israised intempera ture'to 90 C.-and 16'parts of zinc dust SlQW-z ly added, .after which the melt is kept at 90 C. With stirring for 40' minutes. It is then steam distilled in aqueous solution of parts of sodium carbonatejuntil the pyridine is removed and filtered? The solution so obtained is brown and has a'blue fluorescence in dilute solution.

The solution ofthe ester salt so obtained is I evaporated down to about 250 parts and boiled under a reflux condenser with partsof ammonia liquor (about 0.8 8 s. g. )r a ndit I: 1.25 parts of cupricfac'etate. The-colour of carbo'xyliiclacid, maybeisolated if desired eil d d adly. f i he r r m e "stufi's or intermediates, for-instance, by di- I scribed W p 'thefsolution' of the ester salt after'evapora- I the liquor gradually changes to red and the process app-ears to be complete after 2 hours.

The "ester salt W pp e t l alt of. 1'-,amin'o-9: l0-anthra y l by'the usual Qmethods, or the solution may azotiz-ation and coupling by the methods dein co-pending Ur applicationsNos. f

I 2 p v iThisisflsimilar to .Examplel, except that "tion, is boiled with 100'parts of 50 methyl- 7 r 1 chlor-2-carboxyanthraqui-' '7: nonelare mixed with 50 parts of: pyridine sulphurican-hydride and 100 partsof pyri- 'amine and copper acetate instead of with ammonia liquor andccopp'e r acetate.

I Ema/mpl'e V dine and then 16 parts of zinc dust gradually added at 80-85 C1 The melt is then main- 7, taine'd at SO -S5 G. for one hour and steam distilled'with 40 parts of sodium carbonate ,Aftergfiltering off the-zinc residuesfth efil-,

trates' are acidified with acetic acid, whereupon any unchanged' chlorcarboxylic acid is V lpartsfof ammoniumliquor and 15pm of cupric acetatef precipitatedand maybe filtered oil', The

solution which weighs approximately 250 parts," is; treated for-5 hours at the boil; with f-l lfhe dark brown solution" cooled-"and acidified hydrochloric acid and a brown sparingly soluble by-product is removed by r i v filtration The-'filtrate'isof-a light brown colour with a green. fluorescence and appar entlycontains-the disulphuric acid ester salt of,- l-aminoanthraquinone 2 carboxylic acid.

- It-gdiazotizes to a red-brown solution which canb'e cou'pledwith phenols. -f

In each of the foregoingexamples the 1- 'chloroanthraquinone-2-carboxylic acid may I he -replaced by the equivalentquantity of 1- Io 'romoanthra quinone 2carboxylic acid, or of an alkyl' estenof one'iof these' acidsl: The products obtainedin all cases have the gen- 'L'fo+so311 NRR' where iofithe letters R, R' :R" rep:

f6: resents.eitherhydrogenor alkyl.

' 1min be seen that our invention'provides amino compound is ammonia.

a new and convenient method for thelmanuit facture of sulphuric esters of this general 1 formula without the necessity of makingf acylamino-compounds and; s11bsequ t1y hyi drolyzing them limit: ourselves to the specific embodimentsj.

thereof except as defined in the appended I ":1 1 p 7 l;

. fWe claim: .7 L'In'th-e manufacture'ofdisulphuric esters having in the form able formula: V c

H Oa'S- O 'N-ER 7O As many appa'rentlywidely' diflerent em I bodiments' of this invention-may be made without departing from the spirit and scope' thereof, itisto be understood that we do not of the free-aci-d the probv wherein R represents hydrogen or analkyl? group; the step which comprisesreacting an amino compound the prohable formula: V

. H-N V wherein R represents hydrogen or antalky-l resents hydrogen or an alkyl group.

2. The process of claim '1' i nwhi'h the presence sorber.

3. Th-eprocess" of claim in'which o reaction is efl'ected byheating said reactants 7 in an aqueoussolution in the presence sofa copper salt. 7

4; The process of claim 1 in said 5..1heprocess of claim'l" in which said amino compound is'methylamine.

6. The processof claim 1 in which halogenoanthrahy-droquinone compound is a .chloro compound, thesaid 'X representing V chlorine.

v 7. T1 e. process of claim 1 in which" said? i halogenoanthrahydroquinone compound is-1 chloranthrahydroquin-one-fZ-carboxylic acid. 7 8. In the manufacture of disulphuric esters v said re f" actlon 1s efl'ectedin an aqueous medium ln ff ofcopper acetateas an 'acld alohaving in the form of the free acid the probable formula wherein R represents hydrogen or an alkyl group, the step which comprises mixing together an aqueous solution of l-chloroanthraquinone-Q-carboxylic acid, ammonia and a small amount 'of cupricacetate, boiling the K aqueous mixture thus obtained under reflux until reaction and condensation are effected, and then isolating the disulphuric tester salt of 1-amino-9: 10-anthraquinone-2-carboxylic acid. 7

9. In the manufacture ofdisulphuric esters having in the form of the free acid the probable formula:

HOaS-O 1\ITR 1 y 1 T COOR t I I Hots-( group, the process which comprisesreacting a 1-halogeno-2-carboxyanthraquinone compound having the probable formula:

wherein X represents halogen and R represents an alkyl group with pyridine sulphuric anhydride, pyridine and zinc, and then re acting the disulphuric ester of l-halogenoanthraquinone-Q-carboxylic acid compound 11. In the manufacture of disulphuric es ters having in the form of the free acid the probable formula:

wherein R represents hydrogen or an alkyl wherein R represents hydrogen or analkyl group, the process which comprises mixing. together 1-chloro-2-carboxyanthraquinonepyridine sulphuric, anhydride, pyridine and Zinc dust, heating the mixture to between to C. until reaction is effected, steam distilling the reaction mixture thus obtained in an aqueous solution ofsodiumfcarbonate to removethe pyridineffiltering the aqueous solution thus obtained to remove zinc residues -and other insoluble s,,forming an aque ous 7 mixture of. the; di'sulphuric' ester com pound thus obtained, ammonia and copper acetate, heating the aqueous mixture thusob- V tained until reaction and condensation Ware efiected and the-urecovering the disulphuric; acid ester salt of,1aminoanthrahydroquinone-Q-carboXylicacid thus obtained. I

12. he process of'claim' 11 in which after the zinc residues are removed the-filtrate is,

acidified ,with'acetic acid and any precipitated unchanged chloro-carboxylic acid is; filtered off.

is Tlie process ofclaim 11 the amino derivative; is, formed by, thereac;

tion of the ammoniaand rdisulphuric ester compound, the solution is acidified withhydrochloric acid and the acidified solution fil-,

tered to remove sparingly soluble byproducts, thus obtaining a filtrate having a light brown color with a green fluorescence.v

14. In the manufacture of esters having in the form of the free acid the probable formula: V

wherein R represents hydrogen or an alkyl disulphurio I wioo group, the step which comprises reacting'a 1-halogenoanthraquinone-Q-carboxylic having the probable formula:

acid

wherein X represents a halogen and R represents hydrogen or an alkyl group, with' pyridine-sulphuric anhydride, pyridine and zinc dust, and recovering the disulphuric 3' ester of l-halogenoanthrahydroquinone-Q-V carboxylic acid thus-produced. is 7 15. As products useful in the production of dyes and intermediates, amino and alkylamino derivatives of sulphuric esters of anihrahydr0quinoneshaving the probable for mula z" Wherein'R represents hydrogen or enfalkyl. group, 'said esters forming"--light colored aqueous solutions showing a green fluoresv r cence.

' anthrahydrQquin ne-EZ-carboxylic aeid-disulp'huric' ester, said ester 'bein gsoluble in we ter and giving light colored'solutions. 7

"17; As a product, useful in the production V of dyestuifs and intermediates, l-amino- 10- anthrahyclroquinone-2-carboxylie disulph u ric ester, said ester being "soluble" in, Water, giving; light Colored solutions having a green fluorese'nCefa'nd being capable ofdiazotiza- Q ti'on andcouplin'g with phenols.

In testimony whereof we aflix our signatures.-; l

' DJAQWQFAIRW A H R.

JOHN 'THOMAS. 

